Production of artificial masses



Patented June 19, 1934 PATENT OFFICE 1,963,762 PRODUCTION OF ARTIFICIAL MASSES Wilhelm Pungs, Karl Eisenmann, and Erich Scholz, Ludwigshafen-on-the-Bhine, and Theodor .Koilmann, to I. G.

, asslgnora Mannheim, Germany Farbenindustrle Aktlengesellschaft,

Frankfort-on-the-Main, Germany No Drawing. Application November 29, 1930, Serial No. 499,122. In Germany December 6,

6 Claims- (Cl. 260-3) splitting off water, instead of the urea or thiourea,

and formaldehyde. The properties of the resulting products, such as stability to water, solubility, 1 behaviour to other substances and the like, are determined by the choice of the solvent employed for the condensation. Ethers of methylol ureas 5 have been prepared according to the specification of the U. S. Patent No. 1,699,245, which ethers may be converted into resins or lacquers by polymerization in the presence of organic solvents.

We have now found that products of a new kind are obtained by carrying out the condensation of a urea and an aldehyde, preferably with the addition of a small amount of acid or alkaline condensing agents, in the presence of organic substances which contain at least one free hydroxyl group and also at least one reactive group, such as halogen, primary or secondary amino, carboxyl or additional hydroxyl groups, thereby preserving at least one reactive group, and the reactive groups still present then being wholly or partially converted with organic compounds capable of forming an oxygenated linkage with the said reactive group, such as alcoholates, phenols,

i phenolates, acid chlorides or anhydrides, salts of '1 carboxylic acids or alkylene oxides. Thechoice of the last-mentioned substances depends on the desired propertiesof the condensation products,

40 and the substances chosen for the conversion may also be simultaneously or subsequently brought into reaction with other reactive components so far as the products still contain reactive groups such as double linkages. It is possible in this manner to prepare condensation products which are different from the usual resinous condensation products of urea and formaldehyde, the properties of which as regards solubility in organic solvents, homogenization with other non-volatile substances, capability of being moulded by pressing, waterproof nature, fusibility and other physical properties may be adapted to the purpose for which the products are intended. Thus for example, fusible solid or oily products can be obtained as well as products resembling linoxyn or waxes, which, however, have not completely lost the resinous character of artificial resins. The condensation of a urea and an aldehyde is meant to include the condensation of a methylol urea or of an anhydride thereof, whereby about the same products are obtained as on working with a urea and aldehyde; in most cases the employment of a methylol urea will be preferred owing to the possibility of working with lower quantities of solvents. l

Especially suitable agents containing at least one hydroxyl group and another reactive group are for example polyhydric alcohols, as for example ethylene glycol, dior poly-ethylene glycol, glycerol, or their derivatives having at least one hydroxyl group and another reactive group such as monoalkyl or monoaryl ethers of glycerol, halogen substitution products, such as ethylene chlorhydrin, glycerol a-monochlorhydrin or a-s-dichlorhydrin, and esters of polyhydric alcohols with polybasic organic acids, as for example esters of phthalic, oxalic, succinic, adipic or tartaric acid of the type:

oHE-o-oo-ru-c 0-0-0111 (JJHOIDI 01 rnon H.011

or esters of benzoic acid or other monobasic aromatic or aliphatic saturated or unsaturated acids 85 with polyhydric alcohols corresponding to the general formula:

n-ooo-om HIOTI In these formulae, R represents an aliphatic, cycloaliphatic or aromatic hydrocarbon radicle, a: and 11 represent any whole numbers, and 11 may be 0 or any whole numbers. Primary or secondary amines according to the aforesaid definition are the different alkylol amines as for example mono-, dior tri-ethanol or propanol amines, N-ethanol aniline and the like.

The course of some specific reactions according to the present invention may be illustrated by the following formula. In order to facilitate comprehension of these formulae, reference is made only to the monomeric monomethylol urea, it being, however, understood that the invention relates to polymerized monoand di-methylol ureas. In the formulae U denotes the radicle:

1. The condensation of monomethyl urea with glycol proceeds according to the formulae; o-onrorwno-om-cmon-s to give an ester; instead of acetyl chloride also acetic anhydride may beused; 7 (b) with sodium methylate:

to give an ether;

(c) with the acid methyl ester of oxalic acid:

to give a di-ester;

(d) with glycol monoacetate:

to give an ester-ether.

2. The condensation of monomethylol urea with ethylenechlorhydrine proceeds according to the formula:

The latter compound may be reacted according to our invention I v (a) with sodium acetate:

to give an ester;

(b) with sodium methylate:

to give an ether;

(0) with the sodium salt of the acid methyl 3. The condensation of monomethylol urea still present, as for with monoethanolamine proceeds according to the formulae:

' to our invention (a) with acetyl chloride:

v-om-o cnn-nuq i-cm I to give an amide;

to give an ester amide. Similarly, hydroxy-carboxylic acid ('HOR-COOH) with the formation of an ether or ester group the remaining carboxyl, or alcoholic group respectively, being then convertible asset out. In each case the products correspond to the .general formula H- N-ClIz- Oll ZCNllCHz-O RrX-Rz in which :c is an integral number above 1 and Z denotes oxygen or sulphur, R1 indicates an alkyl radicle containing at least2 carbon atoms, in which hydrogen atoms may be substituted by a methylol urea may react with a oxygen, ether or ester radi'cles, and which alkyl radicle R1 is connected to a hydrocarbon radiclc R2 through X which denotes an ether oxygen atom, a carboxyl group, an amine group or a carboxylic amide group, in which hydrocarbon radicle R2 hydrogen atoms may be substituted by hydroxyl, ester or vether groups.- As pointed out above, phenolates or phenols may be employed but the reaction proceeding with phenols has not been definitely ascertained.

In view of the conversion of the reactive groups example by etherification or esterification, it ispreferable not to start with the polyhydric alcohols themselves, but with their halogen substitution products. The halogen content of the condensation products freed from solvent may be readily determined and thus the amount of alcoholate to be employed for the etherification or the amount of sodium salt for the esterification may be calculated. If desired, a partial etherification and partial esteriflcati may be performed, so that mixed ether and ester' productsare obtained, or other kinds of conversion may be effected.

The reaction components may often simultaneously act as solvents when employed in excess and the separation of the excess acting as sol-. vent in the condensation can be effected before the conversion of the reactive groups in the primary products, preferably by precipitation of the condensation product by adding an organic solvent ln 'which'the condensation product is in-. soluble or, when the liquid is sufilciently volatile, by steam distillation.

When the said agent with and in which the condensation is to be carried out is too viscous, it is preferably previously diluted with an inert solvent which contains no free hydroxyl or other reactive groups, as for example dioxane. 1

Example 1 v cubic centimeters of a solution in ethyl alcohol of 5 per cent by weight of urea nitrate are added to 1200 grams of ethylene chlorhydrin and heated to 95 C., 800 grams of dimethylol urea then being slowly introduced while stirring, and the whole stirred for a further 20 minutes at 90 C. After cooling the solution, neutraliz ing with tertiary sodium phosphate and filtering, 5 timesits volume of 95 per cent ethyl alcohol is added while stirring vigorously, the condensation product thus separating in a powdery form. It is washed once with ethyl ether and dried in vacuo at a comparatively elevated temperature of between 40 and 50 C. The chlorine content of the product is 9 per cent.

Urea and paraformaldehyde or trioxymethylene may be used as the initial material instead of dimethylol urea.

250 grams of the product precipitated with alcohol are dissolved in 600 grams of ethylene glycol monomethyl ether and 200 grams of the sodium soap of linseedoil fatty acids are added to the solution. The reaction mixture is then heated at about 120 C. for about 12 hours while stirring and the solution is separated from precipitated sodium, chloride. The, conversion, which is carried out with a quantity of sodium soap slightly exceeding that required for esterification, proceeds practically quantitatively. The smal amount of sodium soap still present in the solution is removed by careful neutralization with a few drops of glacial acetic acid the .linoleic acid set free being then dissolved in the ether. The condensation product esterifled with the linseed oil fatty acids is precipitated by mixing thesolution with from 5 to 6 times its volume of ethyl ether. After repeated washing with ethyl ether and drying, a yellow brown resin having an appearance similar to linoxyn is obtained. A solution thereof in ethylene glycol monomethyl ether leaves behind on a substratum after drying a highly lustrous film, which when in thick layers is pale yellow in colour, having great hardness and adhesive power. The solution may also'be mixed with solutions of nitrocellulose and these mixtures are suitab.e for example as abinding medium for priming masses containing fillers. The condensation product probably corresponds to the formula is the acid radicle of the linseed oil fatty acids an a: is any integral number above 1.

Example 2 200 grams of the solid condensation product having a chlorine content of 9 per cent prepared in ethylene chlorhydrin according to Example 1 are dissolved in 450 grams of ethylene glycol monomethyl ether. 220 grams ofa potassium soap of fatty acids of high molecular weight obtainable by treating deresinified crudc Montan wax with 200 per cent of its weight of chromic acid according to the U. S. Patent No. 1,737,975 are added to the solution. The reaction mixture i then heated at about 116 C. for about 8 hours -while stirring. The solution, while still hot, is

separated from the precipitated potassium chloride and the condensation product esterified with the fatty acids is freed from solvent by distillation in vacuo or with steam. The product is a pale yellow substance, which is faintly translucent when in thick layers and which, in contrast to other urea-formaldehyde condensation products, is fusible. The melting point is 80 C. In its outward appearance the product resembles a wax.

The product may be pressed in the warm state into shaped articles with or without the usual additional materials such as asbestos, saw-' dust, talcum, paper pulp and/or colouring materials. The addition of small amounts of a suitable hardening agent of acid nature such as inorganic or, preferably organic acids, or acid salts or acid esters before pressing, as for example 3 per cent of glycolic acid calculated with reference to the final condensation product, facilitates the hardening of the pressed article. The condensation product probably corresponds to the following formula n which formula is the acid radicle of the montanic acids and .1:

is any integral number above 1.

Example 3 100 parts of adipic l.1-diglyceride (prepared by the conversion of the sodium salt of adipic acid with a-HlOIlOChlOIhYdliIl) are diluted with 40 parts of dioxane, heated to 90 C. and treated with 0.7 part of concentrated hydrochloric acid, 50 parts of dimethylol urea being added then while stirring vigorously. After stirring for half an hour at 90 C., the reaction mixture is neutralized with tertiary sodium phosphate and the condensation product is;precipitated from the filtered and cooled solution by mixing therewith 8 times its volume of 95 per cent ethyl alcohol. A tough plastic product is obtained. 6 parts by weight of this product, after drying at from 40 to 50 C., in vacuo and after pulverizing, are suspended in 100 parts by weightof pyridine. 6 parts by weight of benzoyl chloride are added to the suspension and the mixture is stirred while being cooled with ice until the completion of the conversion. The reaction mixture is then ".poured into water and a pale yellow oil product separates which is washed with water several times. A solution of leaves behind on a substratum after drying a colourless firmly adherent film which maysubsequently be hardened at e1 vated temperatures such as from 100 to high adhesive power the product may advantageously be employed as an adhesive,for example for sticking together strips of paper. The

the product in ethylene glycol monomethyl ether By reason of its ed to 100 C. for 2 hours.

in which a: is any integral number abve 1.

7 Example 4 500 parts of dimethylol urea are added while stirring at C. to 100 parts of alpha-monochlorhydrin together with 1.3 parts of concentrated hydrochloric acid. The reaction mixture is stirred at 90 CT for 30 minutes, whereupon it is neutralized with the aid of tertiary sodium phosphate, the condensation product being then precipitated, after filtering and cooling, in the manner described in Example 3. After drying, 595 parts of a condensation product containing 8.5 per cent of chlorine are obtained. Instead of dim'ethylol urea, dimethylolthiourea or a mixture ofboth may be employed.

100 grams of the resulting product are then fused at 80 C. with 100 parts of m-cresol. After cooling to room temperature, 47 parts of phosphorus oxychloride are added while stirring and externally, cooling with ice. After the evolution of hydrochloric acid has decreased the reaction product is left standing for a few hours. The tough, syrupy product is then freed from acid by heating it with an aqueous solution of sodium bicarbonate heated to 50 C. and subsequently with water, whereupon remainders of cresol are removed by a treatment with steam. After removing water by drying in vacuo at 100 C., a pale yellowish resinous product is obtained which is soluble in ethyl alcohol, acetone and ethylene glycol monomethyl ether and may be worked into .lacquers or priming compositions together with cellulose esters. The condensation product probablycorresponds to the following formula I o cam-0 m-o-cmgno fir-0Q CHI in which .1: is any integral number above 1. Example-5 450 parts of glycerine are kneaded together with 5 parts of oxalic acid and 900 parts of dimethylol. urea, whereupon the mixture is heat- The resulting hard white mass is then pulverized in a suitable mill. 175 parts of the resulting disintegrated product are then dissolved at 100 C. in 200 parts of distilled commercial cresol, whereupon, after cooling C., 4.5 parts of phosphorus pentoxide are added while stirring, the temperature rising thereby to C. After stirring at 95 C. for 1 hour the resulting product, which is a tough, syrupy mass after cooling, is washed with hot 'water until the water shows neutral reaction and is then Y tion product is precipitated. After washing it freed from remainders of cresol by treating it at diminished pressure with steam heated to 180 cording to Example 4 and the alkaline solutions 95 of the products may be employed for impregnat ing or sizing paper, pasteboard and the like. The condensation product probably corresponds to the same formula as the product obtained according to Example 4.

Example 6 117 parts of the solid condensation product containing chlorine described in Example 1 are added to a solution of 47 parts of sodium phenolate in 400 parts of ethylene glycol monomethyl ether, whereupon'the mixture is heated for 2 hours at 115 C. The hot solution is separated from sodium chloride formed and the main portion of the glycol ether is distilled off in vacuo. The remaining concentrated solution is then stirred with 6 times its weight of ethyl ether, whereby the reac-' with ethyl ether and drying in vacuo at 20C. a

brownish resin is obtained, the solution of'which in the aforesaid glycol. ether furnishes highly glossy, hard and strongly adherent coatings. If desired, the resinous product may be worked into lacquers or primers together with cellulose esters. It differs from the products obtained according to Examples 4 and 5 by its msolubility in alkali.

OH l

The condensation product probably to the following formula H --NCH:- on Tod-rm-cm-o-cm-cm-o-QI in which a: is any integral number above 1.

Example 7 corresponds Y group and at least one lected from the class consisting of halogen and solved in ethyl alcohol, whereupon the condensation product is precipitated from its solution with 6 times by weight of the latter of a mixture of equal parts of ethyl alcohol and acetone, the product being 100 parts of the condensation product containing 12 per cent by weight of chlorine are dissolved in 130 parts of ethylene glycol monomethyl ether, whereupon 80 parts of potash salt of palm kernel fatty acids are added andthe whole is stirred for 2 /2 hours at from 110 solution is then separated by filtration from potassium chloride formed and the reaction product is precipitated from the solution by incorporating the latter with 6 times its weight of ethyl ether. A yellow resin is obtained which possesses a high adhesive power and may find useful application in joining sheets of paper, the joint sheets possessing a very high electrical insulating power after hardening by heating to from 100 to 110 C. If the dimethylol thiourea be replaced by a mixture of equal quantities of dimethylol thiourea and dimethylol urea a product is obtained which possesses properties, si ar to those of the product described above. The condensation product probably corresponds to the following formula 0 ll RG- is the acid radicle of the palm kernel fatty acids and a: is any integral number above 1.

What we claim is:

1. The process of producing artificial resins which comprises condensing a urea and formaldehyde to a methylol urea in the presence of an organic substance containing a free hydroxyl further substituent sehydroxyl, and then acting on the ether thus obtained with an organic compound capable of reacting with the said substituent forming an ester or ether, said compound'being selected from the class consisting of metal alcoholates, metal phenolates, metal carboxylates, acid chlorides and acid anhydrides.

2. The process of producing artificial resins which comprises condensing a methylol urea an organic substance containing a free hydroxyl group and at least one further substituent selected from the class consisting of halogen and hydroxyl, and 'then acting on the ether thus obtained with an organic compound capable of reacting with the said substituent forming an ester or ether, said compound being selected from the class consisting of metal alcoholates, metal phenolates, metal carboxylates, acid chlorides and acid anhydrides.

then dried in vacuo at about 20 C.

to 115 C. The

- ing a free hydroxyl group and at least one fur- With' 3. The process of producing artificial resins which comprises condensing dimethylol urea with an organic substance containing a free hydroxyl group and at least one further substituent selected from the class consisting of halogen and hydroxyl, and then acting on the ether thus ob- .tained with an organic compound capable of reacting with the said substituent forming an ester or ether, said compound being selected from the class consisting of metal alcoholates, metal phenolates, metal carboxylates, acid chlorides and acid anhydrides.

4. Resinous condensation products of aureaand formaldehyde suitable for lacquer preparations, adhesives and for molding shaped articles which are esters or ethers of an ether of a polymerized methylol urea, and obtainable by condensing a urea and formaldehyde in the presence of an organic substance containing a free hydroxyl group and at least one further substituent selected from the class consisting of halogen and hydroxyl, and then acting on the ether thus obtained with an organic compound capable of reacting with the said substituent forming an ester or ether, saidcompound being selected from the class consisting of metal alcoholates, metal phenolates, metal carboxylates, acid chlorides and acid anhydrides.

5. Resinous condensation products of a urea and formaldehyde suitable for lacquer preparations,

adhesives and for molding shaped articles which are esters or ethers of an ether of a polymerized methylol urea, and obtainable by condensing a methylol urea with an organic substance containing a free hydroxyl group and at least one further substituent selected from the class consisting of halogen and hydroxyl, and then acting on the ether thus obtained with an organic compound capable of reacting with the said substituent forming an ester or ether, saidcompound being selected from the class consisting of metal alco- 11F holates, metal phenolates, metal carboxylates, acid. chlorides and acid anhydrides.

6. Resinous condensation products of a urea and formaldehyde suitable for lacquer preparations, adhesives and for molding shaped articles which 1? are esters or ethers of an ether of a polymerized methylol urea, and obtainable by condensing dimethylol urea with an organic substance containther substituentselected from the class consisting of halogen and hydroxyl, and their acting on the ether thus obtained with an organic compound capable of reacting with the said substitu-- ent forming an ester or ether, said compound being selected from the class consisting of metal alcoholates, metal phenolates, metal carboxylates, acid chlorides and. acid anhydrides.

WILHELM PUNGS. KARL EISENMANN.

ERICI-I SCHOLZ. THEODOR KOLLMANN. 

